JP2022068119A - Method for producing 1-chloro-2,3,3,3-tetrafluoropropene - Google Patents

Abstract

To provide a method for producing 1224yd at high yield.SOLUTION: According to a method for producing 1-chloro-2,3,3,3-tetrafluoropropene, in the presence of a Cu-containing support catalyst having a carrier and a Cu-containing catalyst supported on the carrier, 1,1-dichloro-2,3,3,3-tetrafluoropropene is allowed to react with hydrogen, to produce 1-chloro-2,3,3,3-tetrafluoropropene. The Cu-containing catalyst includes at least one selected from the group consisting of Cu catalyst and Cu-M catalyst. The Cu catalyst includes a monovalent Cu-bearing compound. The Cu-M catalyst includes a monovalent Cu-bearing compound, and a compound having at least one metal selected from the group consisting of Pd, Pt and Ni or at least one atom selected from the group consisting of Pd, Pt and Ni. The carrier has a BET specific surface area of 400 m2/g or more.SELECTED DRAWING: None

Description

The present invention relates to a method for producing 1-chloro-2,3,3,3-tetrafluoropropene.

1-Chloro-2,3,3,3-tetrafluoropropene (CF ₃ CF = CHCl. HCFO-1224yd; hereinafter also referred to as 1224yd) can be used, for example, as a detergent, a refrigerant, a heat medium, a foaming agent, or a solvent. It can be applied to various uses.

In the present disclosure, for halogenated hydrocarbons, the abbreviation of the compound may be described in parentheses after the compound name. In the present disclosure, the abbreviation is used instead of the compound name as necessary. As the abbreviation, only the number after the hyphen (-) and the lowercase alphabetic part (for example, "HCFO-1224yd" is "1224yd") may be used.

In the example column of Patent Document 1, 1,1-dichloro-2,3,3,3-tetrafluoropropene is used using a Ni—Cu catalyst or a 0.5% Pd-8.5% Cu catalyst. It is disclosed that (CF ₃ CF = CCl ₂ , CFO-1214ya; hereinafter also referred to as 1214ya) is reacted with hydrogen to obtain 1224yd.

US Pat. No. 9,637,429

However, the product specifically described in Patent Document 1 contains a large amount of by-products and unreacted raw materials, and the yield of 1224 yd is low.

Therefore, an object of the present invention is to provide a method for producing 1224 yd with high yield.

As a result of diligent studies, the present inventors have found that the above object can be achieved by adopting the following configuration.

(1) 1,1-dichloro-2,3,3,3-tetrafluoropropene is reacted with hydrogen in the presence of a carrier and a Cu-containing supported catalyst containing a Cu-containing catalyst supported on the carrier, and 1 -A method for producing 1-chloro-2,3,3,3-tetrafluoropropene, which obtains chloro-2,3,3,3-tetrafluoropropene.
The Cu-containing catalyst comprises at least one selected from the group consisting of Cu catalysts and Cu-M catalysts.
The Cu catalyst contains a compound having monovalent Cu and contains
The Cu-M catalyst is a compound having monovalent Cu and at least one metal selected from the group consisting of Pd, Pt and Ni or at least one atom selected from the group consisting of Pd, Pt and Ni. Including compounds with
A method for producing 1-chloro-2,3,3,3-tetrafluoropropene, wherein the carrier has a BET specific surface area of 400 m ² / g or more.
(2) The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to (1), wherein the carrier contains activated carbon.
(3) The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to (1) or (2), wherein the carrier has a BET specific surface area of 1000 m ² / g or more.
(4) The 1-chloro-2 according to any one of (1) to (3), wherein the amount of the Cu-containing catalyst supported is 1 to 20 parts by mass in terms of metal atom with respect to 100 parts by mass of the carrier. , 3, 3, 3-Tetrafluoropropene manufacturing method.
(5) The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to any one of (1) to (4), wherein the reaction temperature of the reaction is 30 to 350 ° C.
(6) The 1-described in any one of (1) to (5), wherein the molar ratio of hydrogen to 1,1-dichloro-2,3,3,3-tetrafluoropropene is 0.1 to 50. A method for producing chloro-2,3,3,3-tetrafluoropropene.
(7) The Cu-containing catalyst is a Cu-M catalyst.
The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to any one of (1) to (6), wherein the Cu-M catalyst contains CuCl.
(8) The Cu-M catalyst comprises a compound having at least one metal selected from the group consisting of Pd and Pt, or at least one atom selected from the group consisting of Pd and Pt (1). )-(7). The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to any one of (7).
(9) The Cu-containing catalyst is a Cu catalyst.
The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to any one of (1) to (6), wherein the Cu catalyst contains CuCl.

According to the present invention, it is possible to provide a method for producing 1224 yd with a high yield.

It is a schematic diagram which shows the reaction apparatus.

The numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.

In 1224yd, there are Z-form and E-form which are geometric isomers depending on the position of the substituent on the carbon-carbon double bond.
In the present disclosure, unless otherwise specified, when compound names or abbreviations for compounds are used, at least one selected from the group consisting of Z-form and E-form is shown. Specifically, a Z-form or an E-form, or a mixture containing a Z-form and an E-form at an arbitrary ratio is shown.
When (E) or (Z) is added after the compound name or the abbreviation of the compound, the (E) form or the (Z) form of the compound is indicated. For example, 1224yd (Z) indicates a Z-form and 1224yd (E) indicates an E-form.

The method for producing 1224yd of the present invention (hereinafter, also simply referred to as “the production method of the present invention”) is a method for producing 1224yd in which 1214ya is reacted with hydrogen in the presence of a predetermined Cu-containing supported catalyst.

The Cu-containing supported catalyst includes a carrier and a Cu-containing catalyst supported on the carrier.
The Cu-containing catalyst contains at least one selected from the group consisting of a Cu catalyst and a Cu-M catalyst, the Cu catalyst contains a compound having a monovalent Cu, and the Cu-M catalyst is a monovalent. It comprises a compound having Cu and a compound having at least one metal selected from the group consisting of Pd, Pt and Ni or a compound having at least one atom selected from the group consisting of Pd, Pt and Ni.
In the following, the Cu catalyst and the Cu-M catalyst will be described first, and then the carrier will be described.

(Cu catalyst)
The Cu catalyst contains a compound having monovalent Cu (monovalent copper).
The Cu catalyst means a catalyst having only Cu as a metal element acting as a catalyst. Specific examples of the compound having monovalent Cu include a salt compound having monovalent Cu, an oxide having monovalent Cu (copper oxide), and a halide having monovalent Cu (copper halide). ) Is preferable, and monovalent Cu (CuCl) chloride is particularly preferable.
The Cu catalyst may contain a compound having a Cu atom in addition to the compound having a monovalent Cu described above.
The compound having a Cu atom is a compound other than the compound having a monovalent Cu, and is a compound having only Cu as a metal element acting as a catalyst.
Specific examples of the compound having a Cu atom include compounds represented by Cu (zero-valent Cu), CuCl ₂ , CuF ₂ , and Cu ₂ X ₄ . X independently represents a halogen ion (for example, Cl ⁻ ), a hydroxide ion, and a nitrate ion. Specific examples of the compound represented by Cu ₂ X ₄ include Cu ₂ Cl (OH) ₃ and Cu ₂ (NO ₃ (OH) ₃ ). Among them, Cu is preferable as the compound having a Cu atom.

The Cu catalyst may contain a small amount of metal elements other than Cu as impurities during the production of the catalyst. Specifically, the content of metal elements other than Cu may be 1000 mass ppm or less in total with respect to the total mass of Cu atoms in the Cu catalyst.
However, this does not apply to metal elements that are clearly not involved in this reaction, such as alkali metals and alkaline earth metals contained as ash in activated carbon used as a carrier. The same applies to the Cu—M catalyst described later in this respect.

(Cu-M catalyst)
The Cu-M catalyst is a compound having monovalent Cu (hereinafter, also referred to as "first component"), at least one metal selected from the group consisting of Pd, Pt and Ni, or Pd. It contains a compound having at least one atom selected from the group consisting of Pt and Ni (hereinafter, these are collectively referred to as "second component").

The first component has the same meaning as the compound having monovalent Cu contained in the Cu catalyst, and the preferable range is also the same.

As the second component, as the metal element acting as a catalyst, it is sufficient to have at least one selected from the group consisting of Pd, Pt and Ni, and a compound of a metal, an oxide and a halide is used. Can be done.
The valence of the second component may be either 0 valence or 1 valence or more. As the valence, 2 to 6 valences are preferable, 2 to 3 valences are more preferable, and 2 valences are particularly preferable.

Specific examples of the compound having at least one atom selected from the group consisting of Pd, Pt and Ni include PdO, PdCl ₂ , PtO, PtO ₂ , PtCl ₂ , PtCl ₄ , H ₂ PtCl ₆ , NiO and NiCl. ₂ is mentioned. As the second component, a compound having a Pd atom or a Pt atom is preferable, and a compound having a Pd atom is particularly preferable, from the viewpoint of improving the yield of 1224 yd.

The first component and the second component may be individually present on the same carrier, or may be present as an alloy.

The Cu-M catalyst may contain components other than the first component and the second component as long as the effects of the present invention are not impaired.
Specific examples of the first component and the components other than the second component include a metal or an atom containing at least one selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Au, Bi, and Al. Examples thereof include compounds having.

In the Cu-M catalyst, the mass ratio (M / Cu) of at least one atom selected from the group consisting of Pd, Pt, and Ni to the Cu atom (hereinafter, these are collectively referred to as "M") is , 1/24 or less is preferable, 1/60 or less is more preferable, 1/70 or less is further preferable, 1/80 or less is particularly preferable, and 1/100 or less is preferable from the viewpoint of improving the yield of 1224 yd, particularly the selectivity. Is the most preferable. The above lower limit is preferably 1/999 or more, more preferably 1/700 or more, and particularly preferably 1/500 or more from the viewpoint of reaction yield.

As the Cu-M catalyst, a catalyst containing CuCl is preferable, and at least one metal selected from the group consisting of CuCl and Pd and Pt, or at least one atom selected from the group consisting of Pd and Pt. A catalyst containing a compound having is particularly preferable.

The Cu-containing catalyst described above includes CuCl and a compound having at least one metal selected from the group consisting of Pd and Pt, or at least one atom selected from the group consisting of Pd and Pt. A catalyst containing CuCl and a Pd metal or a compound having a Pd atom is particularly preferable.

(Carrier)
The BET specific surface area of the carrier is 400 m ² / g or more, preferably 800 m ² / g or more, more preferably 1000 m ² / g or more, and particularly preferably 1200 m ² / g or more. The above upper limit is, for example, 3000 m ² / g.
The BET specific surface area means the nitrogen adsorption specific surface area measured by using the BET method.
The measurement of the BET specific surface area is carried out by an apparatus based on a gas adsorption method using nitrogen gas (for example, "3Flex" manufactured by Micrometric Co., Ltd.). The carrier is dried overnight at 130 ° C. under vacuum using a vacuum drying device (for example, "vacuum low temperature dryer" manufactured by EYELA), and then the BET specific surface area is measured.

As the carrier, a carrier containing activated carbon is preferable, and activated carbon is particularly preferable.
Specific examples of activated carbon include wood, charcoal, fruit gala, coconut shell, peat, lignite, and activated carbon prepared from coal as a raw material. Among them, as the activated carbon, activated carbon prepared from a plant as a raw material is preferable, and coconut shell activated carbon is particularly preferable.
As the carrier shape, molded charcoal having a length of about 2 to 5 mm, crushed coal having a length of about 4 to 50 mesh, and granular coal having a length of 2 to 50 mesh are preferable, and crushed coal having a length of 4 to 20 mesh or crushed coal having a yield of 1224 yd is preferable. Granular coal of 4 to 20 mesh is more preferable, and crushed coal of 4 to 6 mesh or granular charcoal of 4 to 6 mesh is particularly preferable.

The carrier may be subjected to a treatment such as pickling in order to enhance the function of supporting the catalyst.
Specific examples of the method for preparing a carrier carrying a Cu catalyst or a Cu-M catalyst are described in "Heterogeneus Catalysts in Industrial Practice" by Sutterfield, 2nd ed. (McGraw-Hill, New York, 1991), pp. As described in 87 to 112, either a precipitation method or an impregnation method can be mentioned, and the impregnation method is particularly preferable.

In the Cu-containing supported catalyst, the specific surface area of the Cu-containing catalyst can be sufficiently increased and the catalytic activity is excellent. Therefore, the amount of the Cu-containing catalyst supported is 100 parts by mass of the carrier in terms of metal atoms. 0.5 to 50 parts by mass is preferable, 1 to 20 parts by mass is more preferable, 3 to 20 parts by mass is further preferable, and 5 to 10 parts by mass is particularly preferable.
As the Cu-M catalyst described above, a mixture in which the first component and the second component are individually supported on a carrier may be used as a mixture, or a mixture of the first component and the second component may be used as a carrier. May be carried on.

From the viewpoint of improving the activity of the Cu-containing supported catalyst, the Cu-containing supported catalyst may be subjected to a reduction treatment in the process of producing the Cu-containing supported catalyst or before being used.
Specific examples of the reduction treatment include a treatment in which a Cu-containing carrier catalyst and hydrogen are brought into contact with each other.
The temperature of the reduction treatment is preferably 100 ° C. or higher, more preferably 150 ° C. or higher, and particularly preferably 180 ° C. or higher. The upper limit of the temperature is preferably less than 400 ° C, more preferably 370 ° C or lower, further preferably 350 ° C or lower, particularly preferably 300 ° C or lower, and most preferably 280 ° C or lower.
Above all, it is preferable that the Cu-containing supported catalyst is not subjected to the above reduction treatment, or is subjected to the reduction treatment within the above temperature range in the process of producing the Cu-containing supported catalyst or before being used.

1214ya, which is a raw material for the production method of the present invention, can be produced by a known method.
Specific examples of the method for producing 1214ya include 1,1-dichloro-2,2,3,3,3-pentafluoropropane (HCFC-225ca) and 1,1,1-trichloro-2,3,3,3. Examples thereof include a method in which tetrafluoropropane (HCFC-224db) is brought into contact with an alkaline aqueous solution in the presence of a phase transfer catalyst to cause a defluorinated hydrogen or dechlorided hydrogen reaction. Dichloropentafluoropropane (225) containing 225ca can be used in the reaction, and only 225ca in 225 is selectively defluorinated by the phase transfer catalyst. After the reaction, 1214ya can be purified by a known method such as distillation. Impurities may be contained in 1214ya after purification. Examples of the impurities include 1,3-dichloro-1,2,3,3-tetrafluoropropene (1214yb) obtained by defluoridating hydrogen reaction of 225 isomers other than 225ca. The content of impurities is preferably 1000 mass ppm or less with respect to the total mass of 1214ya. The above lower limit is, for example, 0 mass ppm.
As 225 containing 225ca, a commercially available product may be used. Examples of the commercially available product include Asahiclean AK225 (a mixture of 48 mol% of 225ca and 52 mol% of 225 cc manufactured by AGC). Tetrabutylammonium bromide (TBAB) is preferred as the phase transfer catalyst.

In the reaction between 1214ya and hydrogen in the production method of the present invention, the molar ratio of the molar amount of hydrogen used to the molar amount of 1214ya used (molar amount of hydrogen / molar amount of 1214ya) is a yield of 1224yd. From the viewpoint of being able to be higher, 0.1 to 50 is preferable, 0.5 to 50 is more preferable, 0.7 to 20 is further preferable, and 1 to 10 is particularly preferable.

The above reaction is usually carried out using a reactor.
The shape and structure of the reactor are not particularly limited. Specific examples of the reactor include a cylindrical vertical reactor that can be filled with a Cu-containing carrier catalyst in the case of a gas phase reaction described later.
As the amount of catalyst to be filled in the cylindrical vertical reactor, an arbitrary amount is used because the optimum filling length differs depending on the gas linear velocity and the contact time, and generally 10 to 500 cm in the cylindrical vertical reactor. Filled with.

In the case of a liquid phase reaction, the content of the Cu-containing carrier catalyst is preferably 0.1 to 20% by mass, particularly preferably 1 to 10% by mass, based on the total amount of the liquid in the reactor. When the content is 1% by mass or more, the reaction rate is excellent. Further, when the content is 10% by mass or less, the catalyst separation step after the reaction and the stirring efficiency during the reaction are excellent.
Specific examples of the material of the reactor include glass, iron, nickel, stainless steel, iron, and an alloy containing nickel as a main component.
The reactor may be provided with a heating unit such as an electric heater inside. The reactor may have a pod for inserting a thermometer to measure the temperature inside.

The reaction between 1214ya and hydrogen in the production method of the present invention may be either a liquid phase reaction or a gas phase reaction.
The liquid phase reaction means that 1214ya in a liquid state is reacted with hydrogen.
The gas phase reaction means that 1214ya in a gaseous state is reacted with hydrogen.
As described above, in the case of a liquid phase reaction, a gas phase reaction is preferable because the pressure inside the reactor becomes high and a high pressure reaction occurs.
The above reaction may be a batch type, a semi-continuous type or a continuous distribution type.

The liquid phase reaction will be described in detail.
As a specific procedure of the liquid phase reaction, for example, hydrogen is continuously or discontinuously supplied into a reactor in which a mixture of 1214ya and a catalyst exists in a liquid state, and 1224yd produced by the reaction is used in the reactor. Examples thereof include a procedure for continuously or discontinuously extracting from the inside.

The reaction temperature in the liquid phase reaction is preferably 30 ° C. or higher, more preferably 100 ° C. or higher, and even more preferably over 160 ° C. from the viewpoint of yield of 1224 yd. Further, 350 ° C. or lower is preferable, 300 ° C. or lower is more preferable, and less than 225 ° C. is further preferable.
The reaction time in the liquid phase reaction is preferably 0.1 to 100 hours, more preferably 0.5 to 50 hours, and particularly preferably 1 to 20 hours from the viewpoint of the yield of 1224 yd and the production efficiency. The reaction time means the residence time of the raw materials (1214ya and hydrogen) in the reactor. The liquid phase reaction may be carried out in the presence of a solvent, if necessary. Examples of the solvent include linear perfluoroalkyl compounds having 5 to 8 carbon atoms represented by CF ₃ (CF ₂ ) _n CF ₃ (where n in the formula represents an integer of 3 to 6). Be done.

Next, the gas phase reaction will be described in detail.
As a specific procedure for the gas phase reaction, 1214ya, which is a raw material heated to a gas state, and hydrogen are continuously supplied into the reactor, and a Cu-containing carrying catalyst filled in the reactor and a gas state are used. 1214ya and hydrogen in a gaseous state are brought into contact with each other to obtain 1224yd.
A gas (diluted gas) inert to the above reaction may be supplied to the reactor because it is effective for adjusting the flow rate, suppressing by-products, suppressing catalyst deactivation, and the like. Specific examples of the diluent gas include nitrogen, carbon dioxide, helium, and argon. For example, when nitrogen is supplied to the reactor as an inert gas, the molar ratio of the molar amount of hydrogen to the molar amount of nitrogen is preferably 0 or more, more preferably 0.1 or more, still more preferably 0.2 or more.

When a Cu catalyst is used, the reaction temperature (temperature in the reactor) in the gas phase reaction is preferably 30 to 350 ° C., more preferably 100 to 350 ° C., and further preferably 160 to 350 ° C. from the viewpoint of yield of 1224 yd. Preferably, 200 to 300 ° C. is particularly preferable, and 230 to 300 ° C. is most preferable.
When a Cu-M catalyst is used, the reaction temperature (temperature in the reactor) in the gas phase reaction is preferably 30 to 350 ° C., more preferably 100 to 300 ° C., and more preferably 160 to 300 ° C. from the viewpoint of the yield of 1224 yd. Is more preferable, 200 to 300 ° C. is particularly preferable, and 230 to 300 ° C. is most preferable. On the other hand, the reaction temperature is preferably 200 to 280 ° C., more preferably 200 to 250 ° C., and particularly preferably 200 to 225 ° C. from the viewpoint of suppressing the formation of by-products and improving the selectivity of 1224 yd.
The temperature inside the reactor can be controlled by adjusting the temperature and pressure of 1214ya and hydrogen supplied to the reactor. If necessary, the inside of the reactor can be supplementarily heated by an electric heater, a microwave generator, or the like.

The reaction time in the gas phase reaction is preferably 0.1 to 1000 seconds, more preferably 1 to 800 seconds, still more preferably 5 to 600 seconds, and particularly preferably 10 to 500 seconds. When the reaction time is 0.1 to 1000 seconds, the reduction reaction of 1214ya proceeds sufficiently, and the yield of 1224yd becomes higher.
The reaction time corresponds to the residence time of the raw materials 1214ya and hydrogen in the reactor, and can be controlled by adjusting the supply amount (flow rate) of 1214ya and hydrogen to the reactor.

The pressure of the reaction system (pressure in the reactor) in the gas phase reaction is preferably 0 to 2.0 MPa, more preferably 0 to 0.5 MPa. Negative pressure may be used. The pressure in the reactor is particularly preferably normal pressure (atmospheric pressure) from the viewpoint of handleability. In this disclosure, pressure refers to gauge pressure unless otherwise noted.
The pressure in the reactor in the liquid phase reaction is preferably the pressure at which the raw material exists in the reactor as a liquid, more preferably higher than the vapor pressure of the raw material at the reaction temperature, and particularly preferably 0.1 to 10 MPa.

In the production method of the present invention, 1224 yd is obtained as a product. As described above, the obtained 1224yd may be Z-form alone, E-form alone, or a mixture of Z-form and E-form.
When the obtained 1224yd is a mixture of Z-form and E-form, the ratio (Z / E) of the mass of Z-form to the mass of E-form is preferably 1 or more, more preferably 2 or more, still more preferably 5 or more. 10 or more is particularly preferable. The upper limit of the above ratio is, for example, 100.
1224yd (Z) is more chemically stable than 1224yd (E). Therefore, if the mass ratio (Z / E) is at least the above lower limit value, 1224yd can be easily used for various purposes such as a cleaning agent, a refrigerant, a heat medium, a foaming agent, and a solvent.

The product obtained by the production method of the present invention may contain impurities in addition to the target product, 1224yd. Specific examples of the impurities include 2,3,3,3-tetrafluoropropene (CF ₃ CF = CH ₂ , HFO-1234yf; hereinafter also referred to as 1234yf), which is produced by further progressing hydrogenation of 1214ya. Examples thereof include 1,1,1-trifluoropropene (CF ₃ CH = CH ₂ , HFO-1243zf; hereinafter also referred to as 1243zf) and 1,1,1,2-tetrafluoropropane (254eb), which are reduced compounds. ..

The total content of 1234yf, 1243zf and 254eb in the product is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the product. The lower limit of the content is, for example, 0% by mass.
The content of 1224 yd in the product is preferably 45 mol% or more, more preferably 55 mol% or more, further preferably 65 mol% or more, and particularly preferably 80 mol% or more, based on the total mass of the product. .. The upper limit of the content is, for example, 100 mol%.
If the product contains impurities, a treatment may be carried out to separate 1224 yd from the obtained product by a known method such as distillation.

Next, a more detailed embodiment of the gas phase reaction will be described with reference to FIG. The reactor 20 shown in FIG. 1 is an example of a reactor used for a gas phase reaction.
The reactor 20 includes a reactor 1. A supply line 2 of 1214ya, a supply line 3 of hydrogen, and a supply line 4 of nitrogen as a diluting gas are connected to the reactor 1.
The reactor 1 preferably includes a heating unit such as an electric heater.
The supply line 2 of 1214ya and the hydrogen supply line 3 may be separately connected to the reactor 1, or may be connected in front of the reactor 1 and connected to the reactor 1. For example, as shown in FIG. 1, the supply line 2 of 1214ya, the hydrogen supply line 3, and the nitrogen supply line 4 are connected. As a result, the mixture of 1214ya, hydrogen and nitrogen is supplied to the reactor 1 via the mixture supply line 5.

In the reaction apparatus 20 shown in FIG. 1, preheaters (preheaters) 2a, 3a and 4a provided with electric heaters and the like in the supply line 2 of 1214ya, the hydrogen supply line 3 and the nitrogen supply line 4, respectively. Is provided. It is preferable that the 1214ya, hydrogen and nitrogen supplied to the reactor 1 are preheated to predetermined temperatures by the preheaters 2a, 3a and 4a, respectively, and then supplied to the reactor 1. As a result, 1214ya, hydrogen and nitrogen can be efficiently raised to a predetermined reaction temperature inside the reactor 1. The preheaters 2a, 3a and 4a are preferably installed.

An outlet line 7 is connected to the outlet of the reactor 1 via a cooling unit 6 such as a heat exchanger. Further, a water vapor and acid liquid recovery tank 8, an alkaline cleaning device 9, and a dehydration tower 10 are connected to the outlet line 7 in this order.
Acidic substances such as hydrogen chloride and hydrogen fluoride, water vapor, and water are removed from the reaction mixture taken out from the reactor 1 by the treatment from the outlet line 7 onward. The obtained gas is hereinafter referred to as "outlet gas". Each component in the outlet gas is analyzed and quantified by an analyzer such as a gas chromatograph (GC).

For example, the outlet gas in the reduction reaction of 1214ya contains 1224yd.
In this case, examples of the compound other than 1224yd contained in the outlet gas include 1234yf, 1243zf and 254eb in addition to the unreacted raw material 1214ya.

By separating and removing components other than 1224 yd contained in the outlet gas by a known means such as distillation, 1224 yd purified to high purity can be produced.

In the reactor 20, the unreacted 1214ya can be separated from the reaction mixture and the outlet gas discharged from the reactor 1 by distillation or the like and returned to the reactor as a part of the raw material. This can improve the productivity of 1224yd.

Hereinafter, the present invention will be described in more detail by way of example. However, the present invention is not limited to the following examples. Examples 1 to 15 are examples, and example 16 is a comparative example.

<Preparation of Cu-containing carrier catalyst>
<< CuCl-PdCl ₂ supported catalyst (Pd / Cu = 1/100) >>
Copper (I) chloride and palladium (II) chloride were supported on activated carbon by the impregnation method. However, the method for preparing the catalyst is not limited to the impregnation method. Hereinafter, a specific preparation procedure using the impregnation method will be described.
Copper (I) chloride (15 g, manufactured by Nakaraitesk), palladium (II) chloride (0.16 g, manufactured by Genuine Chemicals), ion-exchanged water (300 g), 35% by mass hydrochloric acid (41 g, manufactured by Nakaraitesk), Then, the activated carbon (raw material: coconut husk) (150 g) having a BET specific surface area of 1230 m ² / g measured by the BET method and having a granular shape of 4 to 6 mesh was mixed in a flask and allowed to stand for 12 hours, and then the evaporator was added. Hydrogen chloride and water were distilled off under reduced pressure at 60 ° C. When the ratio (moisture content) of water to the total mass of the obtained carrier catalyst became 30% by mass or less, the carrier catalyst in the flask was transferred to a reaction tube, and then the reaction tube was kept at 200 ° C. and nitrogen. The gas was supplied at 16.7 mL / sec for 16 hours and dried. As a result, a CuCl-PdCl ₂ -supported catalyst supported on activated carbon having a mass ratio (Pd / Cu) of Pd to Cu in terms of metal atoms of 1/100 was obtained. The total amount of Cu and Pd supported in terms of metal atoms was 6 parts by mass with respect to 100 parts by mass of activated carbon.

<< CuCl-PdCl ₂ supported catalyst (Pd / Cu = 1/300) >>
The metal carried on the activated carbon by the same procedure as the above << CuCl-PdCl ₂ carrying catalyst (Pd / Cu = 1/100) >> except that the amount of palladium (II) chloride to be mixed was changed to 0.05 g. A CuCl-PdCl ₂ -supported catalyst having a mass ratio of Pd to Cu (Pd / Cu) of 1/300 in atomic terms was obtained. The total amount of Cu and Pd supported in terms of metal atoms was 6 parts by mass with respect to 100 parts by mass of activated carbon.

<< CuCl-PdCl ₂ supported catalyst (Pd / Cu = 1/600) >>
The metal carried on the activated carbon by the same procedure as the above << CuCl-PdCl ₂ carrying catalyst (Pd / Cu = 1/100) >> except that the amount of palladium (II) chloride to be mixed was changed to 0.03 g. A CuCl-PdCl ₂ -supported catalyst having a mass ratio of Pd to Cu (Pd / Cu) of 1/600 in terms of atomic value was obtained. The total amount of Cu and Pd supported in terms of metal atoms was 6 parts by mass with respect to 100 parts by mass of activated carbon.

<< CuCl-PtCl ₂ supported catalyst (Pt / Cu = 1/40) >>
Copper (I) chloride and platinum (II) chloride were supported on activated carbon by the impregnation method. However, the method for preparing the catalyst is not limited to the impregnation method. Hereinafter, a specific preparation procedure using the impregnation method will be described.
Measured by copper (I) chloride (15 g, manufactured by Nakaraitesk), platinum (II) chloride (0.34 g, manufactured by Genuine Chemicals), 35% by mass hydrochloric acid (320 g, manufactured by Nakaraitesk), and BET method. Granularly molded activated carbon (150 g) of 4 to 6 mesh with a BET specific surface area of 1230 m ² / g is mixed in a flask, allowed to stand for 12 hours, and then hydrogen chloride and water are depressurized at 60 ° C. using an evaporator. Distilled away. When the ratio (moisture content) of water to the total mass of the obtained carrier catalyst became 30% by mass or less, the carrier catalyst in the flask was transferred to a reaction tube, and then the reaction tube was kept at 200 ° C. and nitrogen. The gas was supplied at 16.7 mL / sec for 16 hours and dried. As a result, a CuCl-PtCl ₂ -supported catalyst supported on activated carbon and having a mass ratio of Pt to Cu in terms of metal atom (Pt / Cu) of 1/40 was obtained. The total amount of Cu and Pt supported in terms of metal atoms was 6 parts by mass with respect to 100 parts by mass of activated carbon.

<< CuCl-PtCl ₂ supported catalyst (Pt / Cu = 1/70) >>
Metal atom equivalent supported on activated carbon by the same procedure as the above << Cu-Pt catalyst (Pt / Cu = 1/40) >> except that the amount of platinum (II) chloride to be mixed was changed to 0.19 g. A CuCl-PtCl ₂ -supported catalyst having a mass ratio of Pt to Cu (Pt / Cu) of 1/70 was obtained. The total amount of Cu and Pt supported in terms of metal atoms was 6 parts by mass with respect to 100 parts by mass of activated carbon.

<< CuCl-PtCl ₂ supported catalyst (Pt / Cu = 1/100) >>
Metal atom equivalent supported on activated carbon by the same procedure as the above << Cu-Pt catalyst (Pt / Cu = 1/40) >> except that the amount of platinum (II) chloride to be mixed was changed to 0.14 g. A CuCl-PtCl ₂ -supported catalyst having a mass ratio of Pt to Cu (Pt / Cu) of 1/100 was obtained. The total amount of Cu and Pt supported in terms of metal atoms was 6 parts by mass with respect to 100 parts by mass of activated carbon.

<< CuCl-H ₂ PtCl ₆ supported catalyst (Pt / Cu = 1/40) >>
Copper (I) chloride and hexachloroplatinic (VI) acid hexahydrate were supported on activated carbon by the impregnation method. However, the method for preparing the catalyst is not limited to the impregnation method. Hereinafter, a specific preparation procedure using the impregnation method will be described.
Copper (I) chloride (15 g, manufactured by Nakaraitesk), hexachloroplatinum (VI) acid hexahydrate (0.67 g, manufactured by Genuine Chemicals), ion-exchanged water (75 g), 35% by mass hydrochloric acid (190 g, Nakarai) (Made by Tesk) and granularly molded activated carbon (150 g) of 4 to 6 mesh with a specific surface area of 1230 m ² / g measured by the BET method are mixed in a flask, allowed to stand for 12 hours, and then used with an evaporator. Hydrogen chloride and water were distilled off under reduced pressure at 60 ° C. When the ratio (moisture content) of water to the total mass of the obtained carrier catalyst became 30% by mass or less, the carrier catalyst in the flask was transferred to a reaction tube, and then the reaction tube was kept at 200 ° C. and nitrogen. The gas was supplied at 16.7 mL / sec for 16 hours and dried. As a result, a CuCl—H ₂ PtCl ₆ -supported catalyst supported on activated carbon and having a mass ratio of Pt to Cu in terms of metal atom (Pt / Cu) of 1/40 was obtained. The total amount of Cu and Pt supported in terms of metal atoms was 6 parts by mass with respect to 100 parts by mass of activated carbon.

<< CuCl-PdCl ₂ supported catalyst (Pd / Cu = 1/100, BET: 1243) >>
Copper (I) chloride and palladium (II) chloride were supported on activated carbon by the impregnation method. However, the method for preparing the catalyst is not limited to the impregnation method. Hereinafter, a specific preparation procedure using the impregnation method will be described.
Copper (I) chloride (15 g, manufactured by Nakaraitesk), palladium (II) chloride (0.16 g, manufactured by Genuine Chemicals), ion-exchanged water (300 g), 35% by mass hydrochloric acid (41 g, manufactured by Nakaraitesk), Then, the activated carbon (raw material: coconut husk) (150 g) having a BET specific surface area of 1243 m ² / g measured by the BET method and having a granular shape of 4 to 6 mesh was mixed in a flask and allowed to stand for 12 hours, and then the evaporator was added. Hydrogen chloride and water were distilled off under reduced pressure at 60 ° C. When the ratio (moisture content) of water to the total mass of the obtained carrier catalyst became 30% by mass or less, the carrier catalyst in the flask was transferred to a reaction tube, and then the reaction tube was kept at 200 ° C. and nitrogen. The gas was supplied at 16.7 mL / sec for 16 hours and dried. As a result, the CuCl-PdCl ₂ -supported catalyst (Pd / Cu = 1/100, BET: 1243), which is supported on the activated carbon and has a mass ratio (Pd / Cu) of Pd to Cu in terms of metal atoms of 1/100. Got The total amount of Cu and Pd supported in terms of metal atoms was 6 parts by mass with respect to 100 parts by mass of activated carbon.

<< CuCl-PdCl ₂ supported catalyst (Pd / Cu = 1/100, BET: 953) >>
Copper (I) chloride and palladium (II) chloride were supported on activated carbon by the impregnation method. However, the method for preparing the catalyst is not limited to the impregnation method. Hereinafter, a specific preparation procedure using the impregnation method will be described.
Copper (I) chloride (15 g, manufactured by Nakaraitesk), palladium (II) chloride (0.16 g, manufactured by Genuine Chemicals), ion-exchanged water (300 g), 35% by mass hydrochloric acid (41 g, manufactured by Nakaraitesk), Then, the activated carbon (raw material: coconut husk) (150 g) having a BET specific surface area of 953 m ² / g measured by the BET method and having a granular shape of 4 to 6 mesh was mixed in a flask and allowed to stand for 12 hours, and then the evaporator was added. Hydrogen chloride and water were distilled off under reduced pressure at 60 ° C. When the ratio (moisture content) of water to the total mass of the obtained carrier catalyst became 30% by mass or less, the carrier catalyst in the flask was transferred to a reaction tube, and then the reaction tube was kept at 200 ° C. and nitrogen. The gas was supplied at 16.7 mL / sec for 16 hours and dried. As a result, the CuCl-PdCl ₂ -supported catalyst (Pd / Cu = 1/100, BET: 953), which is supported on the activated carbon and has a mass ratio (Pd / Cu) of Pd to Cu in terms of metal atoms of 1/100. Got The total amount of Cu and Pd supported in terms of metal atoms was 6 parts by mass with respect to 100 parts by mass of activated carbon.

<< CuCl-PdCl ₂ supported catalyst (Pd / Cu = 1/100, BET: 323) >>
Copper (I) chloride and palladium (II) chloride were supported on activated carbon by the impregnation method. However, the method for preparing the catalyst is not limited to the impregnation method. Hereinafter, a specific preparation procedure using the impregnation method will be described.
Copper (I) chloride (15 g, manufactured by Nakaraitesk), palladium (II) chloride (0.16 g, manufactured by Genuine Chemicals), ion-exchanged water (300 g), 35% by mass hydrochloric acid (41 g, manufactured by Nakaraitesk), Then, the activated carbon (raw material: coconut husk) (150 g) having a BET specific surface area of 323 m ² / g measured by the BET method and having a granular shape of 4 to 6 mesh was mixed in a flask and allowed to stand for 12 hours, and then the evaporator was added. Hydrogen chloride and water were distilled off under reduced pressure at 60 ° C. When the ratio (moisture content) of water to the total mass of the obtained carrier catalyst became 30% by mass or less, the carrier catalyst in the flask was transferred to a reaction tube, and then the reaction tube was kept at 200 ° C. and nitrogen. The gas was supplied at 16.7 mL / sec for 16 hours and dried. As a result, the CuCl-PdCl ₂ -supported catalyst (Pd / Cu = 1/100, BET: 323), which is supported on the activated carbon and has a mass ratio (Pd / Cu) of Pd to Cu in terms of metal atoms of 1/100. Got The total amount of Cu and Pd supported in terms of metal atoms was 6 parts by mass with respect to 100 parts by mass of activated carbon.

<reaction>
<< Example 1 >>
Using the same reaction apparatus as the reactor 20 described with reference to FIG. 1, 1214ya was reacted with hydrogen to obtain 1224yd, as described below. In Examples 1 to 11 and 14 to 15, they were used in the reaction without performing the pretreatment for reducing CuCl and PdCl ₂ in the supported catalyst described later.
As the reactor 1, a reaction tube made of SUS304 and having an inner diameter of 35.3 mm installed in an electric furnace was used. A thermometer for measuring the internal temperature was inserted in the sheath tube of the reaction tube. The reaction tube was filled with a CuCl-PdCl ₂ -supported catalyst (Pd / Cu = 1/100) prepared by the above method to a length of 30 cm. The temperature inside the reaction tube was controlled at 180 ° C.
1214ya, hydrogen and nitrogen were continuously supplied to the reactor 1 from supply lines 2, 3 and 4, which are stainless steel tubes, respectively. As the preheaters 2a, 3a and 4a, an electric furnace set to a furnace temperature of 200 ° C. was used. The supply ratios of 1214ya, hydrogen and nitrogen were controlled to be 25 mol%, 25 mol% and 50 mol%, respectively, and supplied to the reactor 1.
The flow rate (supply amount per unit time) of the mixed gas was controlled so that the residence time of the mixed gas (1214ya, hydrogen and nitrogen) inside the reactor 1 was 120 seconds.
The pressure inside the reactor 1 was the same as the atmospheric pressure.

A gas chromatograph (GC) was used for the composition analysis of the obtained product (outlet gas). As the column, DB-1301 (length 60 m × inner diameter 250 μm × thickness 1 μm, manufactured by Agilent Technologies) was used. The ratio (unit:%) of the molar amount of 1224yd in the product to the molar amount of 1214ya supplied to the reactor was determined, and this was defined as "1224yd yield". It can be evaluated that the larger this value is, the higher the yield of 1224 yd is.

<< Example 2 >>
The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 250 ° C.

<< Example 3 >>
Examples except that the reaction temperature was changed to 220 ° C. using a CuCl-PdCl _{2-supported catalyst (Pd / Cu = 1/300) instead of the CuCl-PdCl 2 -} supported catalyst (Pd / Cu = 1/100). The reaction was carried out in the same manner as in 1.

<< Example 4 >>
The reaction was carried out in the same manner as in Example 3 except that the reaction temperature was changed to 250 ° C.

<< Example 5 >>
Examples except that the reaction temperature was changed to 220 ° C. using a CuCl-PdCl ₂ -supported catalyst (Pd / Cu = 1/600) instead of the CuCl-PdCl ₂ -supported catalyst (Pd / Cu = 1/100). The reaction was carried out in the same manner as in 1.

<< Example 6 >>
The reaction was carried out in the same manner as in Example 5 except that the reaction temperature was changed to 250 ° C.

<< Example 7 >>
Examples except that the reaction temperature was changed to 220 ° C. by using a CuCl-PtCl ₂ -supported catalyst (Pt / Cu = 1/40) instead of the CuCl-PdCl ₂ -supported catalyst (Pd / Cu = 1/100). The reaction was carried out in the same manner as in 1.

<< Example 8 >>
A CuCl-H ₂ PtCl ₆ -supported catalyst (Pt / Cu = 1/40) was used instead of the CuCl-PdCl ₂ -supported catalyst (Pd / Cu = 1/100), except that the reaction temperature was changed to 220 ° C. , The reaction was carried out in the same manner as in Example 1.

<< Example 9 >>
The reaction was carried out in the same manner as in Example 8 except that the reaction temperature was changed to 250 ° C.

<< Example 10 >>
Examples except that the reaction temperature was changed to 250 ° C. using a CuCl-PtCl ₂ -supported catalyst (Pt / Cu = 1/70) instead of the CuCl-PdCl ₂ -supported catalyst (Pd / Cu = 1/100). The reaction was carried out in the same manner as in 1.

<< Example 11 >>
Examples except that the reaction temperature was changed to 250 ° C. using a CuCl-PtCl ₂ -supported catalyst (Pt / Cu = 1/100) instead of the CuCl-PdCl ₂ -supported catalyst (Pd / Cu = 1/100). The reaction was carried out in the same manner as in 1.

<< Example 12 >>
Before starting the continuous supply of 1214ya, hydrogen and nitrogen, the reaction tube was kept at 180 ° C., hydrogen gas was supplied at 1.67 mL / sec for 16 hours, and the CuCl-PdCl ₂ carrying catalyst (Pd / Cu = 1). A pretreatment for reducing / 100) was carried out, and the reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 220 ° C. In the obtained 1224yd (Z) selectivity, the 1224yd (Z) selectivity was 64.6% and the 1224yd (E) selectivity was 30.6%.

<< Example 13 >>
In the pretreatment for reducing the CuCl-PdCl ₂ -supported catalyst (Pd / Cu = 1/100), the reaction was carried out in the same manner as in Example 12 except that the reaction tube was kept at 330 ° C. In the obtained 1224yd (Z) selectivity, the 1224yd (Z) selectivity was 53.3% and the 1224yd (E) selectivity was 39.4%.

<< Example 14 >>
The reaction temperature was changed to 220 ° C. by using a CuCl-PdCl ₂ -supported catalyst (Pd / Cu = 1/100, BET: 1243) instead of the CuCl-PdCl ₂ -supported catalyst (Pd / Cu = 1/100). Except for the above, the reaction was carried out in the same manner as in Example 1.

<< Example 15 >>
The reaction temperature was changed to 220 ° C. by using a CuCl-PdCl ₂ -supported catalyst (Pd / Cu = 1/100, BET: 953) instead of the CuCl-PdCl ₂ -supported catalyst (Pd / Cu = 1/100). Except for the above, the reaction was carried out in the same manner as in Example 1.

<< Example 16 >>
The reaction temperature was changed to 220 ° C. by using a CuCl-PdCl ₂ -supported catalyst (Pd / Cu = 1/100, BET: 323) instead of the CuCl-PdCl ₂ -supported catalyst (Pd / Cu = 1/100). Except for the above, the reaction was carried out in the same manner as in Example 1.

The evaluation results are shown in the table.
In the table, "1214ya conversion rate" represents the ratio of the molar amount of converted 1214ya to the molar amount of 1214ya supplied to the reactor.
In the table, "1224yd selectivity", "1234yf selectivity", and "1243zf selectivity" represent the ratio of the molar amount of each obtained compound to the molar amount of converted 1214ya, respectively.

As shown in the table, according to the production method of the present invention, the yield of 1224 yd was improved.
From the comparison between Example 1 and Example 2, when the reaction temperature was 230 ° C. or higher, the yield of 1224 yd was further improved.
Further, from the same comparison, when the reaction temperature was 200 to 225 ° C., the selectivity of 1224 yd was further improved.
From the comparison between Example 2 and Example 11, when the Cu—M catalyst contained a compound having a monovalent Cu and a compound having a Pd metal or a Pd atom, the yield of 1224 yd was further improved.
From the comparison between Example 12 and Example 13, the yield of 1224 yd was further improved when the temperature of the pretreatment for reducing the Cu-containing carrier catalyst was 300 ° C. or lower.
From the comparison between Example 15 and Example 1 or Example 14, the yield of 1224 yd was further improved when the BET specific surface area was 1000 m ² / g or more.
From the comparison between Example 1 and Example 16, when the BET specific surface area was 400 m ² / g or more, the yield of 1224 yd was further improved.

1: Reactor 2: 1214ya supply line 2a: Preheater 3: Hydrogen supply line 3a: Preheater 4: Nitrogen supply line 4a: Preheater 5: Mixture supply line 6: Cooling unit 7: Outlet line 8: Steam And acid liquid recovery tank 9: Alkaline cleaning device 10: Dehydration tower 20: Reaction device

Claims (9)

In the presence of a Cu-containing carrier catalyst containing a carrier and a Cu-containing catalyst supported on the carrier, 1,1-dichloro-2,3,3,3-tetrafluoropropene is reacted with hydrogen to cause 1-chloro. A method for producing 1-chloro-2,3,3,3-tetrafluoropropene, which comprises -2,3,3,3-tetrafluoropropene.
The Cu-containing catalyst contains at least one selected from the group consisting of a Cu catalyst and a Cu-M catalyst.
The Cu catalyst contains a compound having monovalent Cu and contains.
The Cu-M catalyst is a compound having monovalent Cu and at least one metal selected from the group consisting of Pd, Pt and Ni or at least one selected from the group consisting of Pd, Pt and Ni. Including compounds with atoms
A method for producing 1-chloro-2,3,3,3-tetrafluoropropene, wherein the carrier has a BET specific surface area of 400 m ² / g or more. The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to claim 1, wherein the carrier contains activated carbon. The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to claim 1 or 2, wherein the carrier has a BET specific surface area of 1000 m ² / g or more. The 1-chloro-2, according to any one of claims 1 to 3, wherein the supported amount of the Cu-containing catalyst is 1 to 20 parts by mass in terms of metal atom with respect to 100 parts by mass of the carrier. A method for producing 3,3,3-tetrafluoropropene. The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to any one of claims 1 to 4, wherein the reaction temperature of the reaction is 30 to 350 ° C. The 1-chloro according to any one of claims 1 to 5, wherein the molar ratio of the hydrogen to the 1,1-dichloro-2,3,3,3-tetrafluoropropene is 0.1 to 50. -2,3,3,3-A method for producing tetrafluoropropene. The Cu-containing catalyst is the Cu-M catalyst.
The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to any one of claims 1 to 6, wherein the Cu-M catalyst contains CuCl. Claims 1 to 1, wherein the Cu-M catalyst comprises a compound having at least one metal selected from the group consisting of Pd and Pt, or at least one atom selected from the group consisting of Pd and Pt. 7. The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to any one of 7. The Cu-containing catalyst is the Cu catalyst.
The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to any one of claims 1 to 6, wherein the Cu catalyst contains CuCl.

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